Curable solid particulate compositions

ABSTRACT

The present invention relates to curable solid particulate compositions that include: (a) a first reactant having at least two cyclic carbonate groups; and (b) a second reactant having at least two active hydrogen groups that are reactive with the cyclic carbonate groups of the first reactant. With some embodiments, the first reactant is a polyol residue having at least two cyclic carbonate groups, such as bisphenol A that has been reacted with epichlorohydrin, and in which the oxirane groups thereof have been converted to cyclic carbonate groups. The active hydrogen groups of the second reactant, with some embodiments, are each independently selected from hydroxyl groups, thiol groups, and amine groups. The curable solid particulate compositions, with some embodiments, are in the form of curable powder coating compositions.

FIELD OF THE INVENTION

The present invention relates to curable solid particulate compositionsthat include a first reactant having at least two cyclic carbonategroups, and a second reactant having at least two active hydrogen groupsthat are reactive with the cyclic carbonate groups of the firstreactant.

BACKGROUND OF THE INVENTION

Reducing the environmental impact of coatings compositions, inparticular that associated with emissions into the air of volatileorganic compounds during their use, has been an area of ongoinginvestigation and development in recent years. Accordingly, interest inpowder coatings has been increasing due, in part, to their inherentlylow volatile organic content (VOC), which significantly reduces airemissions during the application process. While both thermoplastic andthermosetting powder coatings compositions are commercially available,thermosetting powder coating compositions are typically more desirablebecause of the superior physical properties, such as hardness andsolvent resistance, provided thereby.

Low VOC coatings are particularly desirable in a number of applications,such as the automotive original equipment manufacture (OEM) market,industrial market, and appliance market, due to the relatively largevolume of coatings that are used in such markets. In addition to therequirement of low VOC levels, many manufacturers have strictperformance requirements of the coatings that are used. In the case ofbasecoats, examples of such requirements include good corrosionresistance, substrate adhesion, and overcoat adhesion. In the case oftopcoats, examples of such requirements include good corrosionresistance, adhesion (to undercoats and/or clear coatings appliedthereover), exterior durability, solvent resistance, gloss, andappearance. While liquid coatings can provide such properties, they havethe undesirable drawback of higher VOC levels relative to powdercoatings, which have essentially zero VOC levels.

Curable powder coating compositions are available in a number ofchemistries, such as: powder coating compositions that include epoxidefunctional polymer and epoxide reactive crosslinking agent; carboxylicacid functional polymer and betahydroxyalkylamide functionalcrosslinking agent; and hydroxyl functional polymer and cappedisocyanate functional crosslinking agent. Presently available curablepowder coating compositions can be subject to undesirable properties,such as insufficient storage stability at room temperature.

It would be desirable to develop new curable powder coating compositionsthat provide coatings having performance properties that are at leastthe same as those of presently available liquid and powder coatingcompositions. It would be further desirable that such newly developedpowder coating compositions also possess at least a sufficient degree ofstorage stability at room temperature.

SUMMARY OF THE INVENTION

In accordance with the present invention, there is provided a curablesolid particulate composition comprising: (a) a first reactant having atleast two cyclic carbonate groups; and (b) a second reactant having atleast two active hydrogen groups that are reactive with the cycliccarbonate groups of said first reactant.

In further accordance with the present invention, there is provided amethod of coating a substrate with the curable solid particulatecomposition of the present invention.

In further accordance with the present invention, there is provided acoated substrate that comprises the curable solid particulatecomposition of the present invention in the form of a coating over atleast a portion of at least one surface of the substrate.

The features that characterize the present invention are pointed outwith particularity in the claims, which are annexed to and form a partof this disclosure. These and other features of the invention, itsoperating advantages, and the specific objects obtained by its use willbe more fully understood from the following detailed description inwhich non-limiting embodiments of the invention are illustrated anddescribed.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, the articles “a,” “an,” and “the” include pluralreferents unless otherwise expressly and unequivocally limited to onereferent.

Unless otherwise indicated, all ranges or ratios disclosed herein are tobe understood to encompass any and all subranges or subratios subsumedtherein. For example, a stated range or ratio of “1 to 10” should beconsidered to include any and all subranges between (and inclusive of)the minimum value of 1 and the maximum value of 10; that is, allsubranges or subratios beginning with a minimum value of 1 or more andending with a maximum value of 10 or less, such as but not limited to, 1to 6.1, 3.5 to 7.8, and 5.5 to 10.

As used herein, unless otherwise indicated, left-to-rightrepresentations of linking groups, such as divalent linking groups, areinclusive of other appropriate orientations, such as, but not limitedto, right-to-left orientations. For purposes of non-limitingillustration, the left-to-right representation of the divalent linkinggroup

or equivalently —C(O)O—, is inclusive of the right-to-leftrepresentation thereof,

or equivalently —O(O)C— or —OC(O)—.

Other than in the operating examples, or where otherwise indicated, allnumbers expressing quantities of ingredients, reaction conditions, andso forth used in the specification and claims are to be understood asmodified in all instances by the term “about.”

As used herein, molecular weight values of polymers, such as weightaverage molecular weights (Mw) and number average molecular weights(Mn), are determined by gel permeation chromatography using appropriatestandards, such as polystyrene standards.

As used herein, polydispersity index (PDI) values represent a ratio ofthe weight average molecular weight (Mw) to the number average molecularweight (Mn) of the polymer (i.e., Mw/Mn).

As used herein, the term “polymer” means homopolymers (e.g., preparedfrom a single monomer species), copolymers (e.g., prepared from at leasttwo monomer species), and graft polymers.

As used herein, the term “(meth)acrylate” and similar terms, such as“(meth)acrylic acid ester” means methacrylates and/or acrylates. As usedherein, the term “(meth)acrylic acid” means methacrylic acid and/oracrylic acid.

As used herein, spatial or directional terms, such as “left”, “right”,“inner”, “outer”, “above”, “below”, and the like, relate to theinvention as it is described herein. However, it is to be understoodthat the invention can assume various alternative orientations and,accordingly, such terms are not to be considered as limiting.

As used herein, the terms “formed over,” “deposited over,” “providedover,” “applied over,” “residing over,” or “positioned over,” meanformed, deposited, provided, applied, residing, or positioned on but notnecessarily in direct (or abutting) contact with the underlying element,or surface of the underlying element. For example, a layer “positionedover” a substrate does not preclude the presence of one or more otherlayers, coatings, or films of the same or different composition locatedbetween the positioned or formed layer and the substrate.

As used herein, the term “free flowing” with regard to the curable solidparticulate compositions of the present invention means a curable solidparticulate composition having the handling characteristics of asubstantially dry particulate composition, having a minimum of dumpingor aggregation between individual particles.

As used herein, the terms “hydroxyl” and “hydroxy” both mean —OH groups.

All documents, such as but not limited to issued patents and patentapplications, referred to herein, and unless otherwise indicated, are tobe considered to be “incorporated by reference” in their entirety.

As used herein, recitations of “linear or branched” groups, such aslinear or branched alkyl, are herein understood to include: a methylenegroup or a methyl group; groups that are linear, such as linear C₂-C₂₀alkyl groups; and groups that are appropriately branched, such asbranched C₃-C₂₀ alkyl groups.

As used herein, the term “aliphatic” means groups that are non-aromatic,such as but not limited to alkyl groups.

As used herein, the term “alkyl” means linear or branched alkyl, such asbut not limited to, linear or branched C₁-C₂₀ alkyl, or linear orbranched C₁-C₁₀ alkyl, or linear or branched C₂-C₁₀ alkyl. Examples ofalkyl groups from which the various alkyl groups of the presentinvention can be selected from, include, but are not limited to, methyl,ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl,pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, and decyl. Alkyl groupsof the various components of the present invention can, with someembodiments, include one or more unsaturated linkages selected from—CH═CH— groups and/or one or more —C≡C— groups, provided the alkyl groupis free of two or more conjugated unsaturated linkages. With someembodiments, the alkyl groups are free of unsaturated linkages, such as—CH═CH— groups and —C≡C— groups.

As used herein, the term “cycloaliphatic” means cyclic groups that arenon-aromatic, such as, but not limited to cycloalkyl groups.

As used herein, the term “cycloalkyl” means groups that areappropriately cyclic, such as but not limited to, C₃-C₁₂ cycloalkyl(including, but not limited to, cyclic C₅-C₇ alkyl) groups. Examples ofcycloalkyl groups include, but are not limited to, cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl. The term“cycloalkyl” as used herein also includes: bridged ring polycycloalkylgroups (or bridged ring polycyclic alkyl groups), such as but notlimited to, bicyclo[2.2.1]heptyl (or norbornyl) and bicyclo[2.2.2]octyl;and fused ring polycycloalkyl groups (or fused ring polycyclic alkylgroups), such as, but not limited to, octahydro-1H-indenyl, anddecahydronaphthalenyl.

As used herein, the term “heterocycloaliphatic” means cyclic groups thatare non-aromatic, such as but not limited to heterocycloalkyl groups,and which have at least one hetero atom in the cyclic ring, such as, butnot limited to, O, S, N, P, and combinations thereof.

As used herein, the term “heterocycloalkyl” means groups that areappropriately cyclic, such as but not limited to, C₃-C₁₂heterocycloalkyl groups or C₅-C₇ heterocycloalkyl groups, and which haveat least one hetero atom in the cyclic ring, such as, but not limitedto, O, S, N, P, and combinations thereof. Examples of heterocycloalkylgroups include, but are not limited to, imidazolyl, tetrahydrofuranyl,tetrahydropyranyl, and piperidinyl. The term “heterocycloalkyl” as usedherein also includes: bridged ring polycyclic heterocycloalkyl groups,such as but not limited to, 7-oxabicyclo[2.2.1]heptanyl; and fused ringpolycyclic heterocycloalkyl groups, such as but not limited to,octahydrocyclopenta[b]pyranyl, and octahydro-1H-isochromenyl.

As used herein, the term “aryl” and related terms, such as “aromatic”,means cyclic groups that are aromatic, and includes, but is not limitedto, C₅-C₁₈ aryl, such as but not limited to, C₅-C₁₀ aryl (includingfused ring polycyclic aryl groups). Examples of aryl groups include, butare not limited to, phenyl, naphthyl, and anthracenyl.

As used herein, the term “heteroaryl” and related terms, such as“heteroaromatic”, includes but is not limited to C₅-C₁₈ heteroaryl, suchas but not limited to C₅-C₁₀ heteroaryl (including fused ring polycyclicheteroaryl groups) and means an aryl group having at least one heteroatom (such as but not limited to O, S, and N, and combinations thereof)in the aromatic ring, or in at least one aromatic ring in the case of afused ring polycyclic heteroaryl group. Examples of heteroaryl groupsinclude, but are not limited to, furanyl, pyranyl, pyridinyl,isoquinoline, and pyrimidinyl.

As used herein, remarks with regard to the active hydrogen groups of thesecond reactant being reactive with the cyclic carbonate groups of thefirst reactant, are inclusive of the cyclic carbonate groups of thefirst reactant and the active hydrogen groups of the second reactantbeing reactive with each other.

The first reactant of the curable solid particulate compositions of thepresent invention includes at least two cyclic carbonate groups. Withsome embodiments, and for purposes of non-limiting illustration, thecyclic carbonate groups of the first reactant can be represented by thefollowing Formula (I),

With some embodiments of the present invention, the first reactant isformed from a precursor material that has at least two oxirane groups(such as a polyester having at least two oxirane groups), in which atleast two oxirane groups thereof have been converted to cyclic carbonategroups. More particularly, at least two of the oxirane groups and, withsome embodiments, substantially all of the oxirane groups, of theprecursor material are converted to cyclic carbonate groups.

Conversion of the oxirane groups of the precursor material can beconducted, with some embodiments, in accordance with art-recognizedmethods. For purposes of non-limiting illustration, conversion ofoxirane groups to cyclic carbonate groups is provided in the followinggeneral Scheme (I),

With reference to general Scheme (I) and in accordance with someembodiments, (A) represents a precursor material having n oxirane groupsthat are converted to cyclic carbonate groups, and (B) represents thefirst reactant of the compositions of the present invention having ncyclic oxirane groups. The group R, with some embodiments, represents aresidue of a material to which n oxirane groups are bonded by divalentlinking group L in (A), and to which n cyclic carbonate groups arebonded by divalent linking group L in (B). For purposes of non-limitingillustration, with some embodiments the first reactant is selected froma polyester having at least two cyclic carbonate groups, in which caseand correspondingly R is the polyester (or residue of the polyester).

In accordance with some embodiments, R of precursor material (A) andfirst reactant (B) of Scheme (I) is in each case a residue of a materialselected from vegetable oils, polyols, isocyanurates, polyesters,polyethers, polyurethanes, polymers prepared by free radicalpolymerization, polymers prepared by controlled radical polymerization,and combinations of two or more thereof.

With further reference to general Scheme (I), Subscript n, with someembodiments, is at least 2, such as from 2 to 100, or from 2 to 80, orfrom 2 to 50, or from 2 to 40, or from 2 to 30, or from 2 to 20, or from2 to 10, or from 2 to 5, in each case inclusive of the recited values.Divalent linking group L can, with some embodiments, be selected from abond, a divalent alkyl group, a divalent cycloalkyl group, a divalentheterocycloalkyl group, a divalent aryl group, a divalent heteroarylgroup, and a heteroatom, such as, but not limited to, O, N, S, and P,and combinations of two or more thereof (such as, but not limited to, acombination of a divalent alkyl group and one or more heteroatoms, suchas O, N, S, and P). With some embodiments, divalent linking group L is adivalent methylene oxide group represented by the following Formula(II),

—O—CH₂—  Formula (II)

With some embodiments, the divalent oxygen (—O—) of Formula (II) isbonded to R of (A) and (B), and the divalent methylene group (—CH₂—) isbonded to the oxirane group of (A) and the cyclic carbonate group of(B), of Scheme (I).

Precursor material (A) can be formed in accordance with art-recognizedmethods, such as but not limited to: reaction of an active hydrogenfunctional material (such as, but not limited to, a hydroxyl and/orthiol functional material) with an oxirane functional material having agroup that is reactive with active hydrogen groups (such as, but notlimited to, reactive with hydroxyls and/or thiols); and reaction of anethylenically unsaturated material with an oxygen source, such as, butnot limited to, ozone and a peroxyacid, which converts each (or at leasttwo) ethylencially unsaturated group into an oxirane group.

With some embodiments, precursor material (A) is formed, in accordancewith art-recognized methods, from reaction of: (i) a hydroxyl functionalmaterial R—(OH)_(n), where n is as described above; with (ii) an oxiranefunctional material having at least one oxirane group and a group thatis reactive with the hydroxyls of the hydroxyl functional material, suchas, but not limited to, epichlorohydrin

With some embodiments, when precursor material (A) is the result of thereaction of a hydroxyl functional material R—(OH)_(n) andepichlorohydrin, divalent linking group L is represented by Formula (II)above.

With some further embodiments, precursor material (A) is formed, inaccordance with art-recognized methods, from reaction of: (i) a materialthat includes at least two ethylenically unsaturated groups; and (ii) anoxygen source, such as, but not limited to, a peroxyacid, such as, butnot limited to, haloperoxybenzoic acid, such as m-chloroperoxybenzoicacid. The material that includes at least two ethylenically unsaturatedgroups is, with some embodiments, selected from one or more vegetableoils, such soybean oil, in which case precursor material (A) is anexpoxidized vegetable oil, such as epoxidized soybean oil. As usedherein, the term “vegetable oil” also includes nut oils. With someembodiments, the vegetable oil includes, but is not limited to, palmoil, soybean oil, rapeseed oil, sunflower seed oil, peanut oil,cottonseed oil, palm kernel oil, coconut oil, olive oil, corn oil, grapeseed oil, hazelnut oil, linseed oil, rice bran oil, safflower oil,sesame seed oil, and combinations of two or more thereof.

With some further embodiments, the material that includes at least twoethylenically unsaturated groups (from which precursor material (A) canbe prepared, with some embodiments) is selected from vegetable oilshaving at least two ethylenically unsaturated groups, polyols having atleast two ethylenically unsaturated groups, isocyanurates having atleast two ethylenically unsaturated groups, polyesters having at leasttwo ethylenically unsaturated groups, polyethers having at least twoethylenically unsaturated groups, polyurethanes having at least twoethylenically unsaturated groups, polymers prepared by free radicalpolymerization having at least two ethylenically unsaturated groups, andpolymers prepared by controlled radical polymerization having at leasttwo ethylenically unsaturated groups.

The conversion of oxirane groups of (A) to cyclic carbonate groups of(B), as represented in general Scheme (I), is typically conducted underconditions of elevated temperature (as represented by the term Heat),such as from 70° C. to 140° C., in the presence of gaseous carbondioxide, and optionally a solvent, such as an inert solvent. The carbondioxide can, with some embodiments, be bubbled continuously through thereaction medium. With some further embodiments, a measured quantity ofcarbon dioxide is charged to the reaction optionally under elevatedpressure, such as from 60 to 150 psi. The reaction can be conducted inthe presence of a suitable solvent, such as an alcohol, for example,isobutanol. The reaction is typically conducted in the presence of asuitable catalyst, such as a tetraalkyl ammonium iodide and/ortetraalkyl ammonium bromide, for example, tetrabutylammonium iodideand/or tetrabutylammonium bromide. After art-recognized work-upprocedures, the product (B) is isolated.

With additional reference to general Scheme (I) and in accordance withsome embodiments, (A) represents a precursor monomer having n oxiranegroups bonded thereto, such as a radically polymerizable oxiranefunctional ethylenically unsaturated monomer. Correspondingly, (B)represents a monomer having n cyclic carbonate groups bonded thereto,such as a radically polymerizable cyclic carbonate functionalethylenically unsaturated monomer, from which the first reactant of thecompositions of the present invention can be prepared, such as bycontrolled radical polymerization or free radical polymerization. Withsome non-limiting embodiments where (A) represents a precursor monomerand (B) represents a monomer, subscript n is at least 1, such as from 1to 4, or from 1 to 3, or 1 to 2, inclusive of the recited values.

In accordance with some embodiments, a polymer is prepared by controlledradical polymerization or free radical polymerization from a radicallypolymerizable oxirane functional precursor monomer, such as representedby (A) in Scheme (I). After formation of the polymer, the oxirane groupsof the oxirane functional precursor monomer residues (or units) thathave been incorporated into the polymer backbone, are converted tocyclic carbonate groups, with some embodiments.

In accordance with some embodiments of the present invention, the firstreactant, of the curable particulate composition, is selected from:polyol residues having at least two cyclic carbonate groups;isocyanurates having at least two cyclic carbonate groups; polyestershaving at least two cyclic carbonate groups; polyethers having at leasttwo cyclic carbonate groups; polyurethanes having at least two cycliccarbonate groups; polymers prepared by free radical polymerizationhaving at least two cyclic carbonate groups; polymers prepared bycontrolled radical polymerization having at least two cyclic carbonategroups; and combinations of two or more thereof.

As used herein, the term “polyol residue” and related terms, such as“polyol residues,” “polyol,” and “polyols,” with regard to polyolresidues having at least two cyclic carbonate groups, means residues ofpolyols that are structurally distinguishable from: the polyesterresidues of the polyesters having at least two cyclic carbonate groups;the polyether residues of the polyethers having at least two cycliccarbonate groups; the polyurethane residues of the polyurethanes havingat least two cyclic carbonate groups; polymer residues of the polymersprepared by free radical polymerization having at least two cycliccarbonate groups; and the polymer residues of the polymers prepared bycontrolled radical polymerization having at least two cyclic carbonategroups. With some embodiments, the term “polyol residue” and relatedterms with regard to polyol residues having at least two cycliccarbonate groups, is a non-polymeric material that is free of repeatingmonomer units (or monomer residues).

The polyol residues having at least two cyclic carbonate groups are,with some embodiments, each independently formed from a polyol residuehaving at least two oxirane groups that have been converted to cycliccarbonate groups. The oxirane groups can be converted to cycliccarbonate groups in accordance with art-recognized methods, such asdescribed previously herein with reference to general Scheme (I), inwhich case R represents a polyol residue.

With some embodiments, the polyol residue (from which the polyolresidues having at least two cyclic carbonate groups are formed) is aresidue of a polyol selected from aliphatic polyols and/or aromaticpolyols. In accordance with some further embodiments, the polyol residue(from which the polyol residues having at least two cyclic carbonategroups are formed) is a residue of a polyol selected from glycerin,trimethylolpropane, trimethylolethane, trishydroxyethylisocyanurate,pentaerythritol, ethylene glycol, propylene glycol, trimethylene glycol,butanediol, heptanediol, hexanediol, octanediol,4,4′-(propane-2,2-diyl)dicyclohexanol, 4,4′-methylenedicyclohexanol,neopentyl glycol, 2,2,3-trimethylpentane-1,3-diol,1,4-dimethylolcyclohexane, 2,2,4-trimethylpentane diol,4,4′-(propane-2,2-diyl)diphenol, and 4,4′-methylenediphenol.

The polyol residue, with some embodiments, (from which the polyolresidues having at least two cyclic carbonate groups are formed) is aresidue of a polyol selected from 4,4′-(propane-2,2-diyl)diphenol,4,4′-(propane-2,2-diyl)dicyclohexanol, 4,4′-methylenediphenol,4,4′-methylenedicyclohexanol, and combinations thereof.

The polyol residue having at least two oxirane groups can be formed inaccordance with art-recognized methods. With some embodiments, thepolyol residue having at least two oxirane groups is formed from thereaction of one mole of a polyol having at least two hydroxyl groups,with at least two moles of epichlorohydrin under art-recognized reactionand work-up conditions.

The cyclic carbonate equivalent weight of the polyol residues having atleast two cyclic carbonate groups is, with some embodiments, less thanor equal to 1000 grams/equivalent, such as from 100 to 1000grams/equivalent.

In accordance with some further embodiments of the present invention,the isocyanurates having at least two cyclic carbonate groups, fromwhich the first reactant can be selected, are each independently formedfrom an isocyanurate having at least two oxirane groups that have beenconverted to cyclic carbonate groups. The oxirane groups, of the oxiranefunctional isocyanurate, can be converted to cyclic carbonate groups inaccordance with art-recognized methods, such as described previouslyherein with reference to general Scheme (I), in which case R representsan isocyanurate.

The isocyanurate having at least two oxirane groups is, with someembodiments, tris(2,3-epoxypropyl)isocyanurate. At least two of theoxirane groups of the tris(2,3-epoxypropyl)isocyanurate are converted tocyclic carbonate groups, such as described previously herein withreference to Scheme (I), with some embodiments. With some furtherembodiments, all three of the oxirane groups of thetris(2,3-epoxypropyl)isocyanurate are converted to cyclic carbonategroups, such as described previously herein with reference to Scheme(I).

The cyclic carbonate equivalent weight of the isocyanurates having atleast two cyclic carbonate groups is, with some embodiments, less thanor equal to 1000 grams/equivalent, such as from 100 to 1000grams/equivalent.

In accordance with some additional embodiments of the present invention,the polyesters having at least two cyclic carbonate groups, from whichthe first reactant can be selected, are each individually formed form apolyester having at least two oxirane groups that have been converted tocyclic carbonate groups. With some embodiments, at least two hydroxylgroups of a polyester having at least two hydroxyl groups are reactedwith an oxirane functional material, such as a 1-halo-2,3-epoxy propane,such as epichlorohydrin, so as to form a polyester having at least twooxirane groups, in accordance with art-recognized methods. At least twoof the oxirane groups of the polyester having at least two oxiranegroups can subsequently be converted to cyclic carbonate groups inaccordance with art-recognized methods, such as described previouslyherein with reference to general Scheme (I), in which case R representsa polyester.

Hydroxyl functional polyesters, from which polyesters having at leasttwo cyclic carbonate groups can be prepared, typically have an averageof at least two hydroxyl groups per polyester molecule. Polyestershaving hydroxyl functionality can be prepared by art-recognized methods,which include reacting carboxylic adds (or their anhydrides) having acidfunctionalities of at least 2, and polyols having hydroxyfunctionalities of at least 2. The molar equivalents ratio of carboxylicacid groups to hydroxy groups of the reactants is selected such that theresulting polyester has hydroxyl functionality and a desired molecularweight.

Examples of multifunctional carboxylic acids useful in preparinghydroxyl functional polyesters include, but are not limited to,benzene-1,2,4-tricarboxylic acid, phthalic acid, tetrahydrophthalicacid, hexahydrophthalic acid,endobicyclo-2,2,1,5-heptyne-2,3-dicarboxylic acid, tetrachlorophthalicacid, cyclohexanedioic acid, succinic acid, isophthalic acid,terephthalic acid, azelaic acid, maleic acid, trimesic acid,3,6-dichlorophthalic acid, adipic acid, sebacic acid, and likemultifunctional carboxylic acids.

Examples of polyols useful in preparing hydroxyl functional polyestersinclude, but are not limited to, the polyols recited previously hereinwith regard to the polyols from which the polyol residues having atleast two cyclic carbonate groups can be prepared. With someembodiments, polyols (from which polyesters having at least two cycliccarbonate groups can be prepared) include, but are not limited to,glycerin, trimethylolpropane, trimethylolethane,trishydroxyethylisocyanurate, pentaerythritol, ethylene glycol,propylene glycol, trimethylene glycol, 1,3-, 1,2- and 1,4-butanediols,heptanediol, hexanediol, octanediol, 2,2-bis(4-cyclohexanol)propane,neopentyl glycol, 2,2,3-trimethylpentane-1,3-diol,1,4-dimethylolcyclohexane, 2,2,4-trimethylpentane diol, and likepolyols.

Polyesters having at least two cyclic carbonate groups, from which thefirst reactant can be selected, have an Mn of less than or equal to10,000, such as from 1,000 to 10,000, or from 2,000 to 7,000, with someembodiments. The cyclic carbonate equivalent weight of the polyestershaving at least two cyclic carbonate groups is, with some embodiments,less than or equal to 3000 grams/equivalent, such as from 300 to 2,000grams/equivalent.

With some embodiments, the polyethers having at least two cycliccarbonate groups, from which the first reactant can be selected, areeach individually formed from a polyether having at least two oxiranegroups that have been converted to cyclic carbonate groups. With someembodiments, at least two hydroxyl groups of a polyether having at leasttwo hydroxyl groups are reacted with an oxirane functional material,such as a 1-halo-2,3-epoxy propane, such as epichlorohydrin, so as toform a polyether having at least two oxirane groups, in accordance withart-recognized methods. At least two of the oxirane groups of thepolyether having at least two oxirane groups can subsequently beconverted to cyclic carbonate groups in accordance with art-recognizedmethods, such as described previously herein with reference to generalScheme (I), in which case R represents a polyether.

The polyethers, from which the polyethers having at least two cycliccarbonate groups of the present invention can be prepared, canthemselves be prepared in accordance with art-recognized methods. Withsome embodiments, the polyethers can be prepared from polyols having twoor more hydroxy groups and polyepoxides having two or more epoxidegroups, which are reacted in proportions such that the resultingpolyether has hydroxy functionality or oxirane functionality. Thepolyols and polyepoxides used in the preparation of the epoxidefunctional polyether may be selected from, for example, aliphatic,cycloaliphatic, and aromatic polyols and polyepoxides, and mixturesthereof. Specific examples of polyols include those recited previouslyherein. Polyepoxides useful in preparing the hydroxy functionalpolyether include, with some embodiments, those resulting from thereaction of a polyol and epichlorohydrin. With some embodiments, one ormore of the polyols recited previously herein can be reacted withepichlorohydrin, so as to result in the formation of a polyepoxide. Forpurposes of non-limiting illustration, the hydroxy functional polyethercan be prepared, with some embodiments, from:4,4′-(propane-2,2-diyl)diphenol and the diglycidyl ether of4,4′-(propane-2,2-diyl)diphenol; or4,4′-(propane-2,2-diyl)dicylcohexanol and the diglycidyl ether of4,4′-(propane-2,2-diyl)dicylcohexanol.

The polyethers having at least two cyclic carbonate groups, with someembodiments, can have an Mn of less than 10,000, such as from 1,000 and7,000. The cyclic carbonate equivalent weight of the polyethers havingat least two cyclic carbonate groups is, with some embodiments, lessthan or equal to 3,000 grams/equivalent, such as from 300 and 2,000grams/equivalent.

The polyurethanes having at least two cyclic carbonate groups, fromwhich the first reactant can be selected, with some embodiments, areeach individually formed from a polyurethane having at least two oxiranegroups that have been converted to cyclic carbonate groups. Thepolyurethane having at least two oxirane groups can be prepared from apolyurethane having at least two hydroxyl groups. At least two hydroxygroups of the hydroxy functional polyurethane can be reacted with anoxirane functional material, such as epichlorohydrin, which results information of the polyurethane having at least two oxirane groups. Atleast two of the oxirane groups of the polyurethane having at least twooxirane groups can be converted to cyclic oxirane groups in accordancewith art-recognized methods, such as described previously herein withreference to Scheme-(I), in which case R represents a polyurethane.

Hydroxyl functional polyurethanes can be prepared in accordance withart-recognized methods, such as by reaction of a polyisocyanate havingat least two isocyanate groups, with a polyol having at least twohydroxy groups, with an appropriate molar excess of hydroxyl groups, soas to form a hydroxyl functional polyurethane having at least 2 hydroxylgroups. Examples of polyisocyanates useful in the preparation ofpolyurethane polyols include, with some embodiments, aliphatic,aromatic, cycloaliphatic and heterocyclic polyisocyanates, and mixturesof such polyisocyanates.

Further examples of polyisocyanates useful in the preparation ofpolyurethane polyols include, but are not limited to,toluene-2,4-diisocyanate; toluene-2,6-diisocyanate; diphenylmethane-4,4′-diisocyanate; diphenyl methane-2,4′-diisocyanate;para-phenylene diisocyanate; biphenyl diisocyanate;3,3′-dimethyl-4,4′-diphenylene diisocyanate;tetramethylene-1,4-diisocyanate; hexamethylene-1,6-diisocyanate;2,2,4-trimethyl hexane-1,6-diisocyanate; lysine methyl esterdiisocyanate; bis(isocyanato ethyl)fumarate; isophorone diisocyanate;ethylene diisocyanate; dodecane-1,12-diisocyanate;cyclobutane-1,3-diisocyanate; cyclohexane-1,3-diisocyanate;cyclohexane-1,4-diisocyanate; methyl cyclohexyl diisocyanate;hexahydrotoluene-2,4-diisocyanate; hexahydrotoluene-2,6-diisocyanate;hexahydrophenylene-1,3-diisocyanate;hexahydrophenylene-1,4-diisocyanate;perhydrodiphenylmethane-2,4′-diisocyanate;perhydrodiphenylmethane-4,4′-diisocyanate, and mixtures thereof.

Examples of polyols having at least two hydroxyl groups, from which thehydroxy functional polyurethane can be prepared, include, but are notlimited to, those polyols recited previously herein. With someembodiments, the polyols, from which the hydroxy functional polyurethanecan be prepared, can be selected from those recited previously hereinwith regard to the polyols from which the polyol residues having atleast two cyclic carbonate groups can be prepared. With some furtherembodiments, the polyols, from which the hydroxy functional polyurethanecan be prepared, can be selected from those recited previously hereinwith regard to the hydroxy functional polyester.

The polyurethanes having at least two cyclic carbonate groups, with someembodiments, can have an Mn of less than 10,000, such as from 100 and7,000. The cyclic carbonate equivalent weight of the polyurethaneshaving at least two cyclic carbonate groups is, with some embodiments,less than or equal to 3,000 grams/equivalent, such as from 100 to 2,000grams/equivalent.

With some embodiments, polymers prepared by free radical polymerizationhaving at least two cyclic carbonate groups, from which the firstreactant can be selected, each independently include or have at leasttwo residues of oxirane functional ethylenically unsaturated monomers inwhich the oxirane groups have been converted to cyclic carbonate groups.The oxirane groups of the oxirane functional ethylenically unsaturatedmonomers can be converted to cyclic carbonate groups before and/or afterthe polymer has been prepared by free radical polymerization.

Polymers prepared by free radical polymerization having at least twocyclic carbonate groups can, with some embodiments, be prepared bycopolymerizing epoxide functional ethylenically unsaturated radicallypolymerizable monomer(s), such as a glycidyl functional (meth)acrylate,such as glycidyl(meth)acrylate, with ethylenically unsaturated radicallypolymerizable monomer(s) free of epoxide functionality, such asalkyl(meth)acrylates. Polymers prepared by free radical polymerizationhaving at least two cyclic carbonate groups can, with some furtherembodiments, be prepared by copolymerizing cyclic carbonate functionalethylenically unsaturated radically polymerizable monomer(s), such as acyclic carbonate functional (meth)acrylate, such as(2-oxo-1,3-dioxolan-4-yl)methyl methacrylate, with ethylenicallyunsaturated radically polymerizable monomer(s) free of cyclic carbonatefunctionality, such as alkyl(meth)acrylates.

With some embodiments, the polymers prepared by free radicalpolymerization having at least two cyclic carbonate groups are acrylicpolymers having at least two cyclic carbonate groups.

The conventional free radical polymerization methods by which the cycliccarbonate functional polymer can be prepared involve, with someembodiments, the use of free radical initiators, such as organicperoxides and/or azo type compounds. Optionally, chain transfer agentscan also be used, such as alpha-methyl styrene dimer and/or tertiarydodecyl mercaptan.

Examples of oxirane functional ethylenically unsaturated radicallypolymerizable monomers that can be used, with some embodiments, in thepreparation of the polymers prepared by free radical polymerizationhaving at least two cyclic carbonate groups include, but are not limitedto, glycidyl(meth)acrylate, 3,4-epoxycyclohexylmethyl(meth)acrylate,2-(3,4-epoxycyclohexyl)ethyl(meth)acrylate and allyl glycidyl ether.Examples of cyclic carbonate functional ethylenically unsaturatedradically polymerizable monomers that can be used, with someembodiments, in the preparation of the polymers prepared by free radicalpolymerization having at least two cyclic carbonate groups include, butare not limited to, the previously recited oxirane functional(meth)acrylate monomers, in which the oxirane groups thereof have beenconverted to cyclic carbonate groups in accordance with art-recognizedmethods, such as described previously herein with reference to Scheme(I), such as (2-oxo-1,3-dioxolan-4-yl)methyl methacrylate.

Ethylenically unsaturated radically polymerizable monomer(s) free ofepoxide functionality and free of cyclic carbonate functionality thatcan be used to prepare the polymers prepared by free radicalpolymerization having at least two cyclic carbonate groups include, butare not limited to, vinyl monomers, allylic monomers, olefins, and otherethylenically unsaturated monomers that are radically polymerizable.

Classes of vinyl monomers that are free of oxirane and cyclic carbonatefunctionality include, but are not limited to, (meth)acrylates, vinylaromatic monomers, vinyl halides and vinyl esters of carboxylic acids.With some embodiments, the (meth)acrylates are selected from at leastone of alkyl(meth)acrylates having from 1 to 20 carbon atoms in thealkyl group. Examples of alkyl(meth)acrylates having from 1 to 20 carbonatoms in the alkyl group that can be used include, but are not limitedto, methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate,isopropyl(meth)acrylate, butyl(meth)acrylate, isobutyl(meth)acrylate,tert-butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate,lauryl(meth)acrylate, isobornyl(meth)acrylate, cyclohexyl(meth)acrylateand 3,3,5-trimethylcyclohexyl(meth)acrylate.

Examples of vinyl aromatic monomers that are free of oxirane and cycliccarbonate functionality include, but are not limited to, styrene,p-chloromethylstyrene, divinyl benzene, vinyl naphthalene and divinylnaphthalene. Vinyl halides from which M may be derived include, but arenot limited to, vinyl chloride and vinylidene fluoride. Vinyl esters ofcarboxylic acids that are free of oxirane and cyclic carbonatefunctionality include, but are not limited to, vinyl acetate, vinylbutyrate, vinyl 3,4-dimethoxybenzoate and vinyl benzoate.

As used herein, by “olefin” and like terms is meant unsaturatedaliphatic hydrocarbons having one or more double bonds, such as obtainedby cracking petroleum fractions. Examples of olefins that are free ofoxirane and cyclic carbonate functionality include, but are not limitedto, propylene, 1-butene, 1,3-butadiene, Isobutylene and diisobutylene.

As used herein, by “allylic monomer(s)” is meant monomers containingsubstituted and/or unsubstituted allylic functionality, such as one ormore radicals represented by the following Formula (I),

H₂C═C(R₁)—CH₂—  (I)

With reference to Formula (I), R₁ is hydrogen, halogen or a C₁ to C₄alkyl group. With some embodiments, R₁ is hydrogen or methyl andconsequently Formula (I) represents an unsubstituted (meth)allylradical. Examples of allylic monomers that are free of oxirane andcyclic carbonate functionality include, but are not limited to:(meth)allyl alcohol; (meth)allyl ethers, such as methyl(meth)allylether; allyl esters of carboxylic acids, such as (meth)allyl acetate,(meth)allyl butyrate, (meth)allyl 3,4-dimethoxybenzoate and (meth)allylbenzoate.

Other ethylenically unsaturated radically polymerizable monomers thatare free of oxirane and cyclic carbonate functionality include, but arenot limited to: cyclic anhydrides, such as maleic anhydride,1-cyclopentene-1,2-dicarboxylic anhydride and itaconic anhydride; estersof acids that are unsaturated but do not have alpha, beta-ethylenicunsaturation, such as methyl ester of undecylenic acid; and diesters ofethylenically unsaturated dibasic acids, such as diethyl maleate.

The polymers prepared by free radical polymerization having at least twocyclic carbonate groups (or cyclic carbonate functional polymersprepared by free radical polymerization) can have, with someembodiments, a cyclic carbonate equivalent weight of at least 100grams/equivalent, or at least 200 grams/equivalent. The cyclic carbonateequivalent weight of the polymer is, with some embodiments, less than10,000 grams/equivalent, or less than 5,000 grams/equivalent, or lessthan 1,000 grams/equivalent. The cyclic carbonate equivalent weight ofthe cyclic carbonate functional polymer prepared by free radicalpolymerization can range between any combination of these values,inclusive of the recited values, such as from 100 to 10,000grams/equivalent, or from 200 to 5,000 grams/equivalent, or from 200 to1,000 grams/equivalent, inclusive of the recited values.

The number average molecular weight (Mn) of the polymers prepared byfree radical polymerization having at least two cyclic carbonate groups(or the cyclic carbonate functional polymer prepared by free radicalpolymerization) is with some embodiments at least 250, or at least 500,or at least 1,000, or at least 2,000. The cyclic carbonate functionalpolymer prepared by controlled radical polymerization also has, withsome embodiments, an Mn of less than 16,000, or less than 10,000, orless than 5,000. The Mn of the cyclic carbonate functional polymerprepared by free radical polymerization can, with some embodiments,range between any combination of these values, inclusive of the recitedvalues, such as from 250 to 16,000, or from 500 to 10,000, or from 1,000to 5,000, or from 2,000 to 5,000, inclusive of the recited values.

In accordance with some further embodiments, polymers prepared bycontrolled radical polymerization having at least two cyclic carbonategroups each independently have or include at least two residues ofoxirane functional ethylenically unsaturated monomers in which theoxirane groups have been converted to cyclic carbonate groups. Theoxirane groups of the oxirane functional ethylenically unsaturatedmonomers can be converted to cyclic carbonate groups before and/or afterthe polymer has been prepared by controlled radical polymerization inaccordance with art-recognized methods, such as described previouslyherein with reference to Scheme (I).

Controlled radical polymerization methods include, but are not limitedto, atom transfer radical polymerization (ATRP), single electrontransfer polymerization (SETP), reversible addition-fragmentation chaintransfer (RAFT), and nitroxide-mediated polymerization (NMP).

Controlled radical polymerization, such as ATRP, is described generallyas a “living polymerization,” i.e., a chain-growth polymerization thatpropagates with essentially no chain transfer and essentially no chaintermination. The molecular weight of a polymer prepared by controlledradical polymerization can be controlled by the stoichiometry of thereactants, such as the initial concentration of monomer(s) andinitiator(s). In addition, controlled radical polymerization alsoprovides polymers having characteristics including, but not limited to:narrow molecular weight distributions, such as polydispersity index(PDI) values less than 2.5; and/or well defined polymer chain structure,such as block copolymers and alternating copolymers, with someembodiments.

For purposes of non-limiting illustration of controlled radicalpolymerization processes, the ATRP process will be described in furtherdetail. The ATRP process can be described generally as including:polymerizing one or more radically polymerizable monomers in thepresence of an initiation system; forming a polymer; and isolating theformed polymer. The initiation system includes, with some embodiments:an initiator having a radically transferable atom or group; a transitionmetal compound, such as a catalyst, which participates in a reversibleredox cycle with the initiator; and a ligand, which coordinates with thetransition metal compound. The ATRP process is described in furtherdetail in U.S. Pat. Nos. 5,763,548, 5,789,487, 5,807,937, 6,538,091,6,887,962, and 7,572,874. With some embodiments, the polymers preparedby controlled radical polymerization having at least two cycliccarbonate groups, are prepared generally in accordance with the ATRPmethod disclosed at column 4, line 12, through column 5, line 67 of U.S.Pat. No. 6,265,489 B1, which disclosure is incorporated herein byreference.

With some embodiments, the ATRP initiator is selected from halomethane,methylenedihalide, haloform, carbon tetrahalide,1-halo-2,3-epoxypropane, methanesulfonyl halide, p-toluenesulfonylhalide, methanesulfenyl halide, p-toluenezsulfenyl halide, 1-phenylethylhalide, C₁-C₈-alkyl ester of 2-halo-C₁-C₆-carboxylic acid,p-halomethylstyrene, mono-hexakis (alpha-halo-C₁-C₆-alkyl)benzene,diethyl-2-halo-2-methyl malonate, ethyl 2-bromoisobutyrate and mixturesthereof. With some further embodiments, the initiator isdiethyl-2-bromo-2-methyl malonate.

Catalysts that can be used in some embodiments in preparing polymersprepared by controlled radical polymerization (such as ATRP) having atleast two cyclic carbonate groups, include any transition metal compoundthat can participate in a redox cycle with the initiator and the growingpolymer chain. With some embodiments, the transition metal compound isselected such that it does not form direct carbon-metal bonds with thepolymer chain. Transition metal catalysts useful in the presentinvention may be represented by the following Formula (II),

TM^(n+)X_(t)  (II)

With reference to Formula (II), TM represents the transition metal, t isthe formal charge on the transition metal having a value of from 0 to 7,and X is a counterion or covalently bonded component Examples of thetransition metal (TM) include, but are not limited to, Cu, Fe, Au, Ag,Hg, Pd, Pt, Co, Mn, Ru, Mo, Nb and Zn. Examples of X include, but arenot limited to, halogen, hydroxy, oxygen, C₁-C₆-aloxy, cyano, cyanato,thiocyanato, and azido. With some embodiments, the transition metal isCu(I) and X is a halogen, such as chloride. Accordingly, with someembodiments, a class of transition metal catalysts are the copperhalides, such as Cu(I)Cl. With some embodiments the transition metalcatalyst contains a small amount, such as 1 mole percent, of a redoxconjugate, for example, Cu(II)Cl₂ when Cu(I)Cl is used.

Ligands that can be used in preparing the polymers prepared bycontrolled radical polymerization (such as ATRP) having at least twocyclic carbonate groups, include, but are not limited to compoundshaving one or more nitrogen, oxygen, phosphorus and/or sulfur atoms,which can coordinate to the transition metal catalyst compound, such asthrough sigma and/or pi bonds. Classes of useful ligands include, butare not limited to: unsubstituted and substituted pyridines andbipyridines; porphyrins; cryptands; crown ethers, such as 18-crown-6;polyamines, such as ethylenediamine; glycols, such as alkylene glycols,such as ethylene glycol; carbon monoxide; and coordinating monomers,such as styrene, acrylonitrile and hydroxyalkyl(meth)acrylates. Withsome embodiments, the ligand is selected from one or more substitutedbipyridines, such as 4,4′-dialkylbipyridyls.

In preparing the polymers prepared by controlled radical polymerization(such as ATRP) having at least two cyclic carbonate groups, the amountsand relative proportions of initiator, transition metal compound andligand are those for which ATRP is most effectively performed. Theamount of initiator used can vary widely and is typically present in thereaction medium in a concentration of from 10⁻⁴ moles/liter (M) to 3 M,such as from 10⁻³ M to 10⁻¹ M. As the molecular weight of the cycliccarbonate functional polymer can be directly related to the relativeconcentrations of initiator and monomer(s), the molar ratio of initiatorto monomer is an important factor in polymer preparation, with someembodiments.

The oxirane functional monomers and monomers that are free of oxiranefunctionality, from which the polymers prepared by controlled radicalpolymerization having at least two cyclic carbonate groups can beprepared, include but are not limited to those classes and examplesrecited previously herein with regard to the polymers prepared by freeradical polymerization having at least two cyclic carbonate groups.

The cyclic carbonate functional polymer can, with some embodiments, havepolymer architecture selected from linear polymers, branched polymers,hyperbranched polymers, star polymers, graft polymers, and mixturesthereof. The form, or gross architecture, of the polymer can becontrolled by the choice of initiator and monomers used in itspreparation. Linear cyclic carbonate functional polymers can be preparedby using initiators having one or two radically transferable groups,such as diethyl-2-halo-2-methyl malonate and alpha,alpha′-dichloroxylene. Branched cyclic carbonate functional polymers canbe prepared by using branching monomers, such as monomers containingradically transferable groups or more than one ethylenically unsaturatedradically polymerizable group, such as 2-(2-bromopropionoxy)ethylacrylate, p-chloromethylstyrene and diethyleneglycol bis(methacrylate).Hyperbranched cyclic carbonate functional polymers can be prepared byincreasing the amount of branching monomer used.

Star cyclic carbonate functional polymers can be prepared usinginitiators having three or more radically transferable groups, such ashexakis(bromomethyl)benzene. Star polymers can be prepared byart-recognized core-arm or arm-core methods. In the core-arm method, thestar polymer is prepared by polymerizing monomers in the presence of thepolyfunctional initiator, such as hexakis(bromomethyl)benzene. Polymerchains, or arms, of similar composition and architecture grow out fromthe initiator core, in the core-arm method. With the arm-core method,the arms are prepared separately from the core and can optionally havedifferent compositions, architecture, molecular weight, and PDI's. Thearms can have different cyclic carbonate equivalent weights, and somecan have no cyclic carbonate functionality. After the preparation of thearms, they are attached to the core by art-recognized methods, so as toresult in the formation of an arm-core polymer.

The cyclic carbonate functional polymers prepared by controlled radicalpolymerization can have, with some embodiments, a cyclic carbonateequivalent weight of at least 100 grams/equivalent, or at least 200grams/equivalent. The cyclic carbonate equivalent weight of the polymeris, with some embodiments, less than 10,000 grams/equivalent, or lessthan 5,000 grams/equivalent, or less than 1,000 grams/equivalent. Thecyclic carbonate equivalent weight of the cyclic carbonate functionalpolymer prepared by controlled radical polymerization can range betweenany combination of these values, inclusive of the recited values, suchas from 100 to 10,000 grams/equivalent, or from 200 to 5,000grams/equivalent, or from 200 to 1,000 grams/equivalent, inclusive ofthe recited values.

The number average molecular weight (Mn) of the polymers prepared bycontrolled radical polymerization having at least two cyclic carbonategroups (or the cyclic carbonate functional polymer prepared bycontrolled radical polymerization) is with some embodiments at least250, or at least 500, or at least 1,000, or at least 2,000. The cycliccarbonate functional polymer prepared by controlled radicalpolymerization also has, with some embodiments, an Mn of less than16,000, or less than 10,000, or less than 5,000. The Mn of the cycliccarbonate functional polymer prepared by controlled radicalpolymerization can, with some embodiments, range between any combinationof these values, inclusive of the recited values, such as from 250 to16,000, or from 500 to 10,000, or from 1,000 to 5,000, or from 2,000 to5,000, inclusive of the recited values.

Prior to use in the curable sold particulate compositions of the presentinvention, the ATRP transition metal catalyst and its associated ligandare, with some embodiments, separated or removed from the cycliccarbonate functional polymer. The ATRP catalyst is removed, with someembodiments, prior to conversion of the precursor polymer to the cycliccarbonate functional polymer. Removal of the ATRP catalyst is achieved,with some embodiments, using known methods, including, for example,adding a catalyst binding agent to the mixture of the oxirane functionalpolymer or cyclic carbonate functional polymer, solvent and catalyst,followed by filtering. Examples of suitable catalyst binding agentsinclude, but are not limited to, alumina, silica, clay, or combinationsthereof. A mixture of the oxirane functional polymer or cyclic carbonatefunctional polymer, solvent and ATRP catalyst can be passed through abed of catalyst binding agent, with some embodiments. Alternatively, theATRP catalyst can be oxidized in situ and retained in the oxiranefunctional polymer or cyclic carbonate functional polymer.

Each first reactant of the curable solid particulate compositions of thepresent invention can be prepared, with some embodiments, in the absenceof solvent, such as by a bulk polymerization process. With someembodiments, the first reactant is prepared in the presence of asolvent, such as water and/or an organic solvent Classes of usefulorganic solvents include, but are not limited to, esters of carboxylicadds, ethers, cyclic ethers, C₅-C₁₀ alkanes, C₅-C₈ cycloalkanes,aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, amides,nitrites, sulfoxides, sulfones, and mixtures thereof. Supercriticalsolvents, such as CO₂, C₁-C₄ alkanes and fluorocarbons, can also beemployed. With some embodiments aromatic hydrocarbon solvents are used,such as xylene, and mixed aromatic solvents such as those commerciallyavailable from Exxon Chemical America under the trademark SOLVESSO.

The solvent is removed or separated from the first reactant prior toincorporation of the first reactant into the curable solid particulatecomposition, with some embodiments. The solvent can be removed byart-recognized methods, such as by distillation under conditions ofreduced pressure and, optionally, elevated temperature, with someembodiments.

The first reactant, with some embodiments is present in the curablesolid particulate composition of the present invention in an amount ofat least 50 percent by weight, or at least 70 percent by weight, or atleast 80 percent by weight, based on total weight of resin solids of thecurable solid particulate composition. The curable solid particulatecomposition also, with some embodiments, contains the first reactant inan amount of less than or equal to 98 percent by weight, or less than orequal to 95 percent by weight, or less than or equal to 90 percent byweight, based on total weight of resin solids of the curable solidparticulate composition. The first reactant can, with some embodiments,be present in the curable solid particulate composition of the presentinvention in an amount ranging between any combination of these values,inclusive of the recited values, such as from 50 to 98 percent byweight, or from 70 to 95 percent by weight, or from 80 to 90 percent byweight, in each case based on total weight of resin solids of thecurable solid particulate composition.

The curable solid particulate compositions of the present invention alsoinclude a second reactant having at least two active hydrogen groupsthat are reactive with the cyclic carbonate groups of the firstreactant. With some embodiments, each active hydrogen group of thesecond reactant is independently chosen from hydroxyl groups, thiolgroups, hydrazide groups, and amine groups.

Second reactants having at least two hydroxyl groups can, with someembodiments, be selected from one or more of the hydroxy functionalprecursor or intermediate materials used to prepare the first reactantsas described previously herein. With some embodiments, the secondreactant can be selected from: one or more of the polyols used toprepare the polyol residues having at least two cyclic carbonate groups;one or more of the hydroxy functional polyesters used to prepare thepolyesters having at least two cyclic carbonate groups; one or more ofthe hydroxy functional polyethers used to prepare the polyethers havingat least two cyclic carbonate groups; one or more of the hydroxyfunctional polyurethanes used to prepare the polyurethanes having atleast two cyclic carbonate groups; and combinations thereof.

Second reactants having at least two hydroxyl groups can, with someembodiments, be selected from: polymers prepared by free radicalpolymerization that have at least two hydroxyl groups; or polymersprepared by controlled radical polymerization that have at least twohydroxyl groups. With some embodiments, such polymers include at leasttwo residues of hydroxy functional ethylenically unsaturated monomers,such as, but not limited to, hydroxy functional C₁-C₂₀ linear, branchedor cyclic alkyl(meth)acrylates. Such polymers can be prepared inaccordance with the methods and monomers as described previously hereinwith regard to the first reactant.

Second reactants having at least two thiol groups can be prepared byart-recognized methods. With some embodiments, a hydroxy functionalmaterial, such as described previously herein with regard to the hydroxyfunctional second reactant or hydroxy functional precursor/intermediatematerials from which the first reactant can be prepared, is reacted withepithiochlorohydrin, which results in the formation of an intermediatematerial having at least two thiirane groups. The thiirane groups of theintermediate material can, with some embodiments, be subsequentlyring-opened in accordance with art-recognized methods so as to form amaterial having at least two thiol groups, from which the secondreactant can be chosen.

Each active hydrogen group of the second reactant is, in accordance withsome embodiments, independently selected from amine groups, and eachamine group of the second reactant is independently selected fromprimary amines and secondary amines.

The second reactant, with some embodiments, includes linear or branchedaliphatic amines, cycloaliphatic amines, heterocycloaliphatic amines,aromatic amines, heteroaromatic amines, and combinations of two or morethereof.

In accordance with some further embodiments, the second reactantincludes diaminocyclohexane, 4,4′-methylenedi(cyclohexylamine),4,4′-propane-2,2-diyl)dicyclohexanamine,3,3′-dimethyl-methylenedi(cyclohexylamine),4,4′-(propane-2,2-diyl)dianiline, 4,4′-methylenedianiline, piperazine,N-amino ethyl piperazine,5-amino-1-aminomethyl-1,3,3-trimethyl-cyclohexane, diamino ethane,diamino propane, diaminobutane, diaminopentane, diaminohexane,diaminoheptane, diaminooctane, diaminodecane, diaminoundecane,diaminododecane, dicyanamide, 4,4′-diaminodiphenyl sulfone, melamine,and combinations of two or more thereof.

The second reactant (b) is present, with some embodiments, in thecurable particulate composition of the present invention in an amount ofat least 2 percent by weight, or at least 5 percent by weight, or atleast 10 percent by weight, based on total weight of resin solids of thecurable particulate composition. The second reactant (b) can also, withsome embodiments be present in the curable particulate composition in anamount of less than or equal to 50 percent by weight, or less than orequal to 30 percent by weight, or less than or equal to 20 percent byweight, based on total weight of resin solids of the curable particulatecomposition. The second reactant can be present in the curableparticulate composition of the present invention in an amount rangingbetween any combination of these values, inclusive of the recitedvalues, such as from 2 to 50 percent by weight, or from 5 to 30 percentby weight, or from 10 to 20 percent by weight, based on total weight ofresin solids of the curable particulate composition, and, inclusive ofthe recited values.

The first reactant (a) is present in the curable solid particulatecomposition, with some embodiments, in an amount of from 50 to 98percent by weight, based on total resin solids weight of the curablesolid particulate composition; and the second reactant is present in thecurable solid particulate composition, with some embodiments, in anamount of from 2 to 50 percent by weight, based on total resin solidsweight of the curable solid particulate composition.

To achieve a suitable level of cure with the curable solid particulatecomposition of the present invention, the equivalent ratio of cycliccarbonate equivalents of the first reactant (a) to active hydrogenequivalents of the second reactant (b) is, with some embodiments, from0.7:1 to 2:1, or from 0.8:1 to 1.3:1.

The curable solid particulate composition of the present invention canalso, with some embodiments, include pigments and fillers. Examples ofpigments include, but are not limited to: inorganic pigments, such astitanium dioxide and iron oxides; organic pigments, such asphthalocyanines, anthraquinones, quinacridones and thioindigos; andcarbon blacks. Examples of fillers include, but are not limited to:silica, such as precipitated silicas; clay; and barium sulfate. Whenused in the composition of the present invention, pigments and fillerscan, with some embodiments, be present in amounts of from 0.1 percent to70 percent by weight, based on the total weight of the curable solidparticulate composition.

The curable solid particulate composition of the present invention can,with some embodiments, optionally contain additives such as, but notlimited to: waxes for flow and wetting; flow control agents, such aspoly(2-ethylhexyl)acrylate; degassing additives such as benzoin;adjuvant resin to modify and optimize coating properties; antioxidants;and ultraviolet (UV) light absorbers. Examples of useful antioxidantsand UV light absorbers include, but are not limited to, those availablecommercially from BASF under the trademarks IRGANOX and TINUVIN. Theseoptional additives, when used, can be present in amounts up to 20percent by weight, based on total weight of the curable solidparticulate composition.

The curable solid particulate composition of the present invention can,with some embodiments, be prepared by first dry blending the firstreactant (a), the second reactant (b), and, optionally, additives, suchas flow control agents, degassing agents, antioxidants and UV absorbingagents, in a dry blender, such as a HENSCHEL blade dry blender. The dryblender is operated for a period of time that is at least sufficient toresult in a homogenous dry blend of the materials charged thereto. Thehomogenous dry blend is then melt blended in a melt blender, such as anextruder, such as a twin screw co-rotating extruder, operated within atemperature range of 80° C. to 140° C., or from 100° C. to 125° C. Theextrudate of the curable solid particulate composition of the presentinvention is cooled and, when used as a powder coating composition, istypically milled to an average particle size of from 15 to 40 microns,or from 20 to 30 microns, with some embodiments.

The first reactant and second reactant of the curable solid particulatecomposition of the present invention are each independently: resinousand having a glass transition temperature (Tg); or crystalline andhaving a crystalline melting point. By “resinous” is meant that thereactant is composed of a majority of amorphous domains, and, canoptionally have some crystalline domains. By “crystalline” is meant thatthe reactant has a majority of crystalline domains, and, optionallysome, such as a minority, of amorphous domains. With some embodiments, acrystalline reactant of the curable solid particulate compositionincludes some amorphous domains.

The curable solid particulate compositions of the present invention,with some embodiments, melt and flow when exposed to elevatedtemperature, such as under conditions of cure. In accordance with somefurther embodiments, when exposed to elevated temperature, such as underconditions of cure, the curable solid particulate compositions of thepresent invention melt and flow, substantially uniformly, so as to formcoatings having substantially uniform thicknesses and, optionally,smooth surfaces.

One or more components of the curable particulate compositions, such asthe first reactant and/or the second reactant, are crystalline materialsthat have lower melt viscosities relative to the melt viscosities of aresinous component or material (having a Tg rather than a meltingpoint). The lower melt viscosity of the crystalline material can, withsome embodiments, reduce the overall melt viscosity of the curable solidparticulate compositions of the present invention, when they are exposedto elevated temperature, such as under conditions cure, which can resultin improved flow and appearance of the resulting cured product, such asa cured coating. With some embodiments, the first and/or secondreactants are crystalline materials independently having a meltviscosity of from 5 centipoise (cps) to 75 cps, such as from 7 cps to 60centipoise (cps), or from 10 cps to 50 cps, as measured at a temperatureof 100° C. using an appropriate device, such as an REL heated cone andplate viscometer commercially available from Research Equipment Ltd.

With some embodiments, the first and/or second reactants are resinousmaterials (having a Tg) which each independently have a melt viscosityof from 10 to 100 poise, or from 20 to 80 poise, or from 30 to 70 poise,as measured at a temperature of 125° C. to 150° C., using an appropriatedevice, such as an REL heated cone and plate viscometer commerciallyavailable from Research Equipment Ltd.

The glass transition temperatures and/or melting points of the firstand/or second reactants can be determined in accordance withart-recognized methods. With some embodiments, glass transitiontemperature values and melting point values are determined usingdifferential scanning calorimetry (DSC) in accordance withart-recognized analytical methods.

In accordance with some embodiments, the first reactant and the secondreactant are each resinous materials and each independently have glasstransition temperatures (determined by DSC analysis) of from 30° C. to80° C., or from 35° C. to 50° C. With some embodiments, at least one ofthe first reactant and the second reactant is a resinous material.

With some embodiments, one of the first reactant and the second reactantis a crystalline material, and the other of the first reactant and thesecond reactant is a resinous material. The crystalline first reactantor crystalline second reactant can, with some embodiments, have amelting point (as determined by DSC analysis) of at least 80° C. andless than or equal to 300° C., or at least 100° C. and less than orequal to 300° C., or at least 110° C. and less than or equal to 200° C.,or at least 115° C. and less than or equal to 150° C., or at least 120°C. and less than or equal to 130° C., inclusive of the recited values,any combination of these recited lower and upper values, and anyintervening values.

With some embodiments, the first reactant is resinous and has a glasstransition temperature, such as of from 30° C. to 80° C., or from 35° C.to 50° C., as measured by DSC.

With some further embodiments, the first reactant is crystalline and hasa crystalline melting point, such as at least 80° C. and less than orequal to 300° C., or at least 100° C. and less than or equal to 300° C.,or at least 110° C. and less than or equal to 200° C., or at least 115°C. and less than or equal to 150° C., or at least 120° C. and less thanor equal to 130° C., inclusive of the recited values, any combination ofthese recited lower and upper values, and any intervening values, asdetermined by DSC.

The curable solid particulate composition of the present invention can,with some embodiments, be free flowing.

The curable solid particulate composition of the present invention canbe cured by any suitable methods. With some embodiments, the curablesolid particulate composition is thermosetting, and is curable byexposure to elevated temperature. As used herein, by “cured” is meant athree-dimensional crosslink network formed by covalent bond formation,such as between the cyclic oxirane groups of the first reactant and theactive hydrogen groups of the second reactant. The temperature at whichthe thermosetting composition of the present invention is cured isvariable and depends in part on the amount of time during which curingis conducted. With some embodiments, the thermosetting composition iscured at a temperature within the range of 80° C. to 204° C., or from149° C. to 204° C., or from 154° C. to 177° C., for a period of 20 to 60minutes.

In accordance with some further embodiments, the curable solidparticulate composition of the present invention is a powder coatingcomposition. With some further embodiments, the curable solidparticulate composition of the present invention is a thermosettingpowder coating composition.

The curable solid particulate composition of the present invention can,with some embodiments be used to coat a substrate, such as when it is inthe form of a curable powder coating composition. The present inventionalso relates to a method of coating a substrate that involves: (a)applying to the substrate a thermosetting composition; (b) coalescingthe thermosetting composition to form a substantially continuous film;and (c) curing the thermosetting composition by exposure to elevatedtemperature. The thermosetting composition includes, or is defined by,the curable solid particulate composition of the present invention aspreviously described herein.

The curable solid particulate composition of the present invention canbe applied, with some embodiments, to the substrate by any appropriateart-recognized methods. With some embodiments, the curable solidparticulate composition (which can be a thermosetting composition withsome embodiments) is in the form of a dry powder, such as a powdercoating, and is applied by spray application. Alternatively, the drypowder can be slurried in a liquid medium such as water, and sprayapplied. As used herein, the term “curable solid particulatecomposition” means a curable solid particulate composition that can bein dry powder form or in the form of a slurry that includes one or moreliquids, such as water and, optionally, one or more organic solvents,such as alcohols.

When the substrate is electrically conductive, the curable solidparticulate composition can be electrostatically applied, with someembodiments. Electrostatic spray application generally involves drawingthe curable solid particulate composition from a fluidized bed andpropelling it through a corona field. The particles of the curable solidparticulate composition become charged as they pass through the coronafield and are attracted to and deposited upon the electricallyconductive substrate, which is grounded. As the charged particles beginto build up, the substrate becomes insulated, thus, limiting furtherparticle deposition. This insulating phenomenon can limit the film buildof the deposited composition to a maximum of 3 to 6 mils (75 to 150microns), with some embodiments.

Alternatively, when the substrate is not electrically conductive, forexample, as is the case with many plastic substrates, the substrate ispreheated prior to application of the curable solid particulatecomposition, with some embodiments. The preheated temperature of thesubstrate is equal to or greater than that of the melting point of thecurable solid particulate composition, but less than its curetemperature, with some embodiments. With spray application overpreheated substrates, film builds of the curable solid particulatecomposition in excess of 6 mils (150 microns) can be achieved, such as10 to 20 mils (254 to 508 microns). Substrates that can be coated by themethod of the present invention include, but are not limited to: metalsubstrates, such as ferrous substrates and aluminum substrates; plasticsubstrates, such as sheet molding compound based plastics; inorganicsubstrates, such as ceramic substrates, and glass substrates comprisingsilica-based glass; wood; and combinations of two or more thereof.

After application to the substrate, the curable solid particulatecomposition of the present invention is then coalesced to form asubstantially continuous film, with some embodiments. Coalescing of theapplied curable solid particulate composition is generally achievedthrough the application of heat at a temperature equal to or greaterthan that of the melting point of the curable solid particulatecomposition, but less than its cure temperature. In the case ofpreheated substrates, the application and coalescing steps can beachieved in essentially one step.

The coalesced curable solid particulate composition of the presentinvention is next cured by the application of heat. The temperature atwhich the curable solid particulate composition of the present inventionis cured is variable and depends in part on the amount of time duringwhich curing is conducted. Temperatures at which the curable solidparticulate composition can be cured include, but are not limited to,those temperatures and ranges as recited previously herein, such as from80° C. to 204° C., or from 149° C. to 204° C., or from 154° C. to 177°C., for a period of 20 to 60 minutes.

The curable solid particulate composition of the present invention canbe applied as a single layer or multiple layered coating, in which eachlayer has the same or different compositions. The curable solidparticulate composition of the present Invention can be applied inconjunction with one or more other coating compositions, such as, butnot limited to, primers, base coats, and/or clear coatings. The curablesolid particulate compositions of the present invention can be used toform (or as) primers, base coats, and/or clear coatings. As used herein,the term “clear coatings” includes, with some embodiments, transparenttop coats. Coatings formed from the curable solid particulatecompositions of the present invention can, with some embodiments, have athickness of from 0.5 to 6 mils (13 to 150 microns), or from 1 to 3 mils(25 to 75 microns).

The present invention is more particularly described in the followingexamples, which are intended to be illustrative only, since numerousmodifications and variations therein will be apparent to those skilledin the art. Unless otherwise specified, all parts and percentages are byweight.

EXAMPLES Synthesis Example A

A bis(cyclic carbonate) of the diglycidyl ether of4,4′-(propane-2,2-diyl)diphenol was prepared using the materials andrelated amounts as summarized in the following Table A-1.

TABLE A-1 Weight (grams) diglycidyl ether of4,4′-(propane-2,2-diyl)diphenol⁽¹⁾ 400 tetrabutylammonium bromide 10triphenyl phosphite 1.2 1-methoxy-2-propanol⁽²⁾ 266 ⁽¹⁾Obtainedcommercially from Momentive under the tradename EPON 880 liquid epoxyresin. ⁽²⁾Obtained commercially from Dow Chemical Company under thetradename DOWANOL PM solvent.

The Ingredients as listed in the above Table A-1 were charged to a 1gallon stainless steel pressure reactor that was equipped with anoverhead stirrer, gas inlet, outlet pipes, a heating jacket,thermocouple, and pressure gauge. The reactor was closed and chargedwith gaseous CO₂ to a pressure of 50 psi. With constant stirring at arate of 500 rpm, the contents of the reactor were heated to and held at130° C. for 4.5 hours. The contents of the reactor were subjected todistillation at reduced pressure, after which the reduced solidscontents of the reactor were removed therefrom.

The cyclic carbonate functional product of Synthesis Example A wasanalyzed by NMR and it was determined that 87 percent of the glycidylether groups of the diglycidyl ether of 4,4′-(propane-2,2-diyl)diphenolfeed material had been converted to cyclic carbonate groups. The cycliccarbonate functional product of Synthesis Example A was found to have asolids of 70.3 percent by weight, as determined at a temperature of 110°C. for 60 minutes. For reference, a schematic representation ofSynthesis Example A is provided in the following Scheme (II).

With reference to Scheme (II), product (A-II) had a melt viscosity of 16centipoise (cps) as measured at a temperature of 100° C. using an RELheated cone and plate viscometer commercially available from ResearchEquipment Ltd.

With reference to Scheme (II), starting material (A-I) and product(A-II) were analyzed by differential scanning calorimetry (DSC), and themelting points for each are summarized in the following Table A-2. Priorto measuring the melting point by DSC, the bis(cyclic carbonate) product(A-II) was placed in an oven at 100° C. for 30 minutes to drive ofremaining solvent. The dried bis(cyclic carbonate) product (A-II) wasfound to have a solids of 98 percent by weight. The DSC analysis wasconducted using a TAI Discovery DSC apparatus. In each case, specimenswere sealed in aluminum hermetic pans, which were subjected to thefollowing sequence of cooling and heating: (i) cooling to −90° C.;heating to 175° C.; cooling to −90° C.; and heating to 175° C. Heatingwas conducted in each case at a rate of 20° C./minute. The DSC wasoperated with a nitrogen purge rate of 50 mL/minute, and was calibratedwith indium, tin, and zinc standards. Melting points were determinedmanually from the final heating cycle.

TABLE A-2 Material Melting Point (A-I) −42° C. (A-II) 128° C.

Synthesis Example B

A bis(cyclic carbonate) of the diglycidyl ether of4,4′-(propane-2,2-diyl)dicyclohexanol was prepared using the materialsand related amounts as summarized in the following Table B-1.

TABLE B-1 Weight (grams) diglycidyl ether of4,4′-(propane-2,2-diyl)dicyclohexanol⁽³⁾ 400 tetrabutylammonium bromide10 triphenyl phosphite 1.2 butyl acetate 266 ⁽³⁾Obtained commerciallyfrom Momentive under the tradename EPONEX 1510 liquid epoxy resin.

The ingredients as listed in the above Table B-1 were charged to a 1gallon stainless steel pressure reactor that was equipped with anoverhead stirrer, gas inlet, outlet pipes, a heating Jacket,thermocouple, and pressure gauge. The reactor was dosed and charged withgaseous CO₂ to a pressure of 50 psi. With constant stirring at a rate of500 rpm, the contents of the reactor were heated to and held at 130° C.for 4.5 hours. The contents of the reactor were subjected todistillation at reduced pressure, after which the reduced solidscontents of the reactor were removed therefrom.

The cyclic carbonate functional product of Synthesis Example B wasanalyzed by NMR and it was determined that 91 percent of the glycidylether groups of the diglycidyl ether of4,4′-(propane-2,2-diyl)dicyclohexanol feed material had been convertedto cyclic carbonate groups. The cyclic carbonate functional product ofSynthesis Example B was found to have a solids of 66.8 percent byweight, as determined at a temperature of 110° C. for 60 minutes. Forreference, a schematic representation of Synthesis Example B is providedin the following Scheme (III).

With reference to Scheme (III), product (B-II) had a melt viscosity of10 centipoise (cps) as measured at a temperature of 100° C. using an RELheated cone and plate viscometer commercially available from ResearchEquipment Ltd.

With reference to Scheme (III), starting material (B-I) and product(B-II) were analyzed by differential scanning calorimetry (DSC), and themelting points for each are summarized in the following Table B-2. Priorto measuring the melting point by DSC, the bis(cyclic carbonate) product(B-II) was placed in an oven at 100° C. for 30 minutes to drive ofremaining solvent. The dried bis(cyclic carbonate) product (B-II) wasfound to have a solids of 98 percent by weight, at determined at 160° C.for 5 minutes. The melting points recited in Table B-2 were determinedin accordance with the DSC analysis as described with regard to TableA-2 previously herein.

TABLE B-2 Material Melting Point (B-I) −42° C. (B-II)  84° C.

Curable Composition Examples Curable Composition 1

A metal panel was preheated to a temperature of 200° C. on anickel-plated hotplate having a surface temperature of 200° C. Thebis(cyclic carbonate) product (A-II) of Synthesis Example A was placedin an oven at 100° C. for 30 minutes to drive of remaining solvent. Thedried bis(cyclic carbonate) product (A-II) was found to have a solids of98 percent by weight.

The dried bis(cyclic carbonate) product (A-II) of Synthesis Example Aand dicyanamide were mixed together on the preheated panel, while stillon the hotplate, in a stoichiometric ratio of 1:1, in a weight totalingabout 50 grams. The composition was mixed by hand using a stainlesssteel spatula on the preheated panel for about 10 seconds. The mixedmolten composition was then drawn-down on the preheated panel using adraw-down bar so as to form a film having a thickness of 5 mils (127micrometers). The metal panel with film drawn-down thereon was removedfrom the hotplate and allowed to cool and solidify.

Additional coated panels were prepared in accordance with the abovemethod, and placed in an oven at a temperature of 93° C. (200° F.) for 5minutes and 25 minutes, and an oven at a temperature of 160° C. (320°F.) for 5 minutes and 25 minutes. The panels were removed from the ovenand allowed to cool to room temperature, after which they were subjectedto double rubs by hand using a red-rag saturated with methyl ethylketone (MEK), which had been drawn over a human index finger. Theresults of the MEK double rub testing are summarized in the followingTable 1.

Comparative Curable Composition 1

Metal panels were coated with a molten composition composed of the feedmaterial (A-I) of Synthesis Example A and dicyanamide (in astoichiometric ratio of 1:1) in accordance with the description providedfor Curable Composition 1 above. The coated metal panels were placed inan oven at a temperature of 93° C. (200° F.) for 5 minutes and 25minutes, and an oven at a temperature of 160° C. (320° F.) for 5 minutesand 25 minutes. The panels were removed from the oven and allowed tocool to room temperature, after which they were subjected to double rubsby hand using a red-rag saturated with methyl ethyl ketone (MEK), whichhad been drawn over a human index finger. The results of the MEK doublerub testing are summarized in the following Table 1.

TABLE 1 MEK Double Rub Results Oven Exposure Comparative CurableConditions Composition 1 Curable Composition 1  5 min @93° C.   0.5 MEKdouble rubs  70 MEK double rubs 25 min @93° C.   5 MEK double rubs +100MEK double rubs  5 min @160° C.  10 MEK double rubs +100 MEK double rubs25 min @160° C. +100 MEK double rubs +100 MEK double rubs

Films having MEK double rub values of +100 showed no change in visualappearance (by naked eye) after being subjected to 100 double rubs, andwere considered to be fully cured. Films having MEK double rub values ofless than 100 (e.g., 10 MEK double rubs) were considered to be less thanfully cured because the film was observed to have disappeared (i.e., tohave been fully solubilized by the MEK) after the indicated number ofdouble rubs.

With reference to Table 1, Curable Composition 1, which is anon-limiting representative embodiment of the present invention,provided films having a significantly improved cure response relative toComparative Curable Composition 1. Films prepared from CurableComposition 1 were observed to have been fully cured after 25 minutes at93° C., relative to films prepared from Comparative Curable Composition1, which were not observed to have obtained full cure until 25 minutesat 160° C.

Curable Composition 2

The bis(cyclic carbonate) product (B-II) of Synthesis Example B wasplaced in an oven at 100° C. for 30 minutes, to drive off remainingsolvent. The resulting dried bis(cyclic carbonate) product (B-II) wasfound to have a solids of 98 percent by weight, as determined at 160° C.for 5 minutes. Metal panels were coated with a molten compositioncomposed of the dried bis(cyclic carbonate) product material (B-II) ofSynthesis Example B and dicyanamide (in a stoichiometric ratio of 1:1)in accordance with the description provided for Curable Composition 1above.

The coated metal panels were placed in an oven at a temperature of 93°C. (200° F.) for 5 minutes and 25 minutes, and an oven at a temperatureof 160° C. (320° F.) for 5 minutes and 25 minutes. The panels wereremoved from the oven and allowed to cool to room temperature, afterwhich they were subjected to double rubs by hand using a red-ragsaturated with methyl ethyl ketone (MEK), which had been drawn over ahuman index finger. The results of the MEK double rub testing aresummarized in the following Table 2.

Comparative Curable Composition 2

Metal panels were coated with a molten composition composed of the feedmaterial (B-I) of Synthesis Example B and dicyanamide (in astoichiometric ratio of 1:1) in accordance with the description providedfor Curable Composition 1 above. The coated metal panels were placed inan oven at a temperature of 93° C. (200° F.) for 5 minutes and 25minutes, and an oven at a temperature of 160° C. (320° F.) for 5 minutesand 25 minutes. The panels were removed from the oven and allowed tocool to room temperature, after-which they were subjected to double rubsby hand using a red-rag saturated with methyl ethyl ketone (MEK), whichhad been drawn over a human index finger. The results of the MEK doublerub testing are summarized in the following Table 2.

TABLE 2 MEK Double Rub Results Oven Exposure Comparative CurableConditions Composition 2 Curable Composition 2  5 min @93° C.  0 MEKdouble rubs  30 MEK double rubs 25 min @93° C.  5 MEK double rubs +100MEK double rubs  5 min @160° C. 10 MEK double rubs +100 MEK double rubs25 min @160° C. 50 MEK double rubs +100 MEK double rubs

As discussed with regard to the MEK double rub results presented inTable 1, and with reference to Table 2, films having MEK double rubvalues of +100 showed no change in visual appearance (by naked eye)after being subjected to 100 double rubs, and were considered to befully cured. Films having MEK double rub values of less than 100 (e.g.,10 MEK double rubs) were considered to be less than fully cured becausethe film was observed to have disappeared (i.e., to have been fullysolubilized by the MEK) after the indicated number of double rubs.

With reference to Table 2, Curable Composition 2, which is anon-limiting representative embodiment of the present invention,provided films having a significantly improved cure response relative toComparative Curable Composition 2. Films prepared from CurableComposition 2 were observed to have been fully cured after 25 minutes at93° C., relative to films prepared from Comparative Curable Composition2, which were not observed to have obtained full cure after 25 minutesat 160° C.

The above results demonstrate that curable compositions according to thepresent invention provide improved cure response, such as full cure atlower temperatures, relative to comparative compositions that haveoxirane functional reactants rather than cyclic carbonate functionalreactants.

The present invention has been described with reference to specificdetails of particular embodiments thereof. It is not intended that suchdetails be regarded as limitations upon the scope of the inventionexcept insofar as and to the extent that they are included in theaccompanying claims.

What is claimed is:
 1. A curable solid particulate compositioncomprising: (a) a first reactant having at least two cyclic carbonategroups; and (b) a second reactant having at least two active hydrogengroups that are reactive with the cyclic carbonate groups of said firstreactant.
 2. The curable solid particulate composition of claim 1,wherein said first reactant is selected from, polyol residues having atleast two cyclic carbonate groups, isocyanurates having at least twocyclic carbonate groups, polyesters having at least two cyclic carbonategroups, polyethers having at least two cyclic carbonate groups,polyurethanes having at least two cyclic carbonate groups, polymersprepared by free radical polymerization having at least two cycliccarbonate groups, polymers prepared by controlled radical polymerizationhaving at least two cyclic carbonate groups, and combinations of two ormore thereof.
 3. The curable solid particulate composition of claim 2,wherein polyol residues having at least two cyclic carbonate groups areeach independently formed from a polyol residue having at least twooxirane groups that have been converted to cyclic carbonate groups. 4.The curable solid particulate composition of claim 3, wherein saidpolyol residue is a residue of a polyol selected from glycerin,trimethylolpropane, trimethylolethane, trishydroxyethylisocyanurate,pentaerythritol, ethylene glycol, propylene glycol, trimethylene glycol,butanediol, heptanediol, hexanediol, octanediol,4,4′-(propane-2,2-diyl)dicyclohexanol, 4,4′-methylenedicyclohexanol,neopentyl glycol, 2,2,3-trimethylpentane-1,3-diol,1,4-dimethylolcyclohexane, 2,2,4-trimethylpentane diol,4,4′-(propane-2,2-diyl)diphenol, 4,4′-methylenediphenol, andcombinations thereof.
 5. The curable solid particulate composition ofclaim 4, wherein said polyol is selected from4,4′-(propane-2,2-diyl)diphenol, 4,4′-(propane-2,2-diyl)dicyclohexanol,4,4′-methylenediphenol, 4,4′-methylenedicyclohexanol, and combinationsthereof.
 6. The curable solid particulate composition of claim 2,wherein isocyanurates having at least two cyclic carbonate groups areeach independently formed from an isocyanurate having at least twooxirane groups that have been converted to cyclic carbonate groups. 7.The curable solid particulate composition of claim 6, wherein saidisocyanurate having at least two oxirane groups istris(2,3-epoxypropyl)isocyanurate.
 8. The curable solid particulatecomposition of claim 2, wherein, polyesters having at least two cycliccarbonate groups are each individually formed from a polyester having atleast two oxirane groups that have been converted to cyclic carbonategroups, polyethers having at least two cyclic carbonate groups are eachindividually formed from a polyether having at least two oxirane groupsthat have been converted to cyclic carbonate groups, and polyurethaneshaving at least two cyclic carbonate groups, are each individuallyformed from a polyurethane having at least two oxirane groups that havebeen converted to cyclic carbonate groups.
 9. The curable solidparticulate composition of claim 2, wherein, polymers prepared by freeradical polymerization having at least two cyclic carbonate groups eachindependently comprise at least two residues of oxirane functionalethylenically unsaturated monomers in which the oxirane groups have beenconverted to cyclic carbonate groups, and polymers prepared bycontrolled radical polymerization having at least two cyclic carbonategroups each independently comprise at least two residues of oxiranefunctional ethylenically unsaturated monomers in which the oxiranegroups have been converted to cyclic carbonate groups.
 10. The curablesolid particulate composition of claim 1, wherein each active hydrogengroup of said second reactant is independently chosen from hydroxylgroups, thiol groups, and amine groups.
 11. The curable solidparticulate composition of claim 10, wherein each active hydrogen groupof said second reactant is independently selected from amine groups, andeach amine group of said second reactant is independently selected fromprimary amines and secondary amines.
 12. The curable solid particulatecomposition of claim 11, wherein said second reactant comprises at leastone of linear or branched aliphatic amines, cycloaliphatic amines,heterocycloaliphatic amines, aromatic amines, and heteroaromatic amines.13. The curable solid particulate composition of claim 12, wherein saidsecond reactant comprises at least one of diaminocyclohexane,4,4′-methylenedi(cyclohexylamine),4,4′-(propane-2,2-diyl)dicyclohexanamine,3,3′-dimethyl-methylenedi(cyclohexylamine),4,4′-(propane-2,2-diyl)dianiline, 4,4′-methylenedianiline, piperazine,N-amino ethyl piperazine,5-amino-1-aminomethyl-1,3,3-trimethyl-cyclohexane, diamino ethane,diamino propane, diaminobutane, diaminopentane, diaminohexane,diaminoheptane, diaminooctane, diaminodecane, diaminoundecane,diaminododecane, dicyanamide, 4,4′-diaminodiphenyl sulfone, andmelamine.
 14. The curable solid particulate composition of claim 1,wherein the ratio of cyclic carbonate equivalents of said first reactantto amine equivalents of said second reactant is from 0.7:1 to 2:1. 15.The curable solid particulate composition of claim 1, wherein said firstreactant is present in said curable solid particulate composition in anamount of from 50 to 98 percent by weight, based on total resin solidsweight, and said second reactant is present in said curable solidparticulate composition in an amount of from 2 to 50 percent by weight,based on total resin solids weight.
 16. The curable solid particulatecomposition of claim 1, wherein said first reactant is resinous and hasa glass transition temperature.
 17. The curable solid particulatecomposition of claim 1, wherein said first reactant is crystalline andhas a crystalline melting point.
 18. The curable solid particulatecomposition of claim 1, wherein said curable solid particulatecomposition is free flowing.
 19. The curable solid particulatecomposition of claim 18, wherein said curable solid particulatecomposition is a powder coating composition.
 20. The curable solidparticulate composition of claim 1, wherein said curable solidparticulate composition is thermosetting.